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WO2007032295A1 - Film stratifié - Google Patents

Film stratifié Download PDF

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Publication number
WO2007032295A1
WO2007032295A1 PCT/JP2006/317951 JP2006317951W WO2007032295A1 WO 2007032295 A1 WO2007032295 A1 WO 2007032295A1 JP 2006317951 W JP2006317951 W JP 2006317951W WO 2007032295 A1 WO2007032295 A1 WO 2007032295A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating liquid
laminated film
weight
resin
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2006/317951
Other languages
English (en)
Japanese (ja)
Inventor
Yasushi Takada
Masato Yanagibashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to KR1020087008709A priority Critical patent/KR101244471B1/ko
Priority to CN2006800412378A priority patent/CN101300294B/zh
Priority to US11/991,836 priority patent/US7972700B2/en
Priority to EP20060797777 priority patent/EP1942132B1/fr
Priority to JP2006529407A priority patent/JP4973187B2/ja
Publication of WO2007032295A1 publication Critical patent/WO2007032295A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
    • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
    • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]

Definitions

  • the present invention relates to a laminated film provided with a laminated film comprising a specific resin and a crosslinking agent, and more specifically for display applications such as a liquid crystal television, a plasma display television, and a rear projection television.
  • the present invention relates to an easily adhesive film for optical use and excellent adhesiveness to various coatings.
  • Thermoplastic resin films are magnetic because they have excellent properties such as mechanical properties, electrical properties, dimensional stability, heat resistance, transparency, and chemical resistance. It is widely used as a base film for many purposes such as recording materials, packaging materials, electrical insulating materials, various photographic materials, photosensitive materials, heat-sensitive materials, graphic arts materials, and the like. In particular, coupled with recent advances in IT technology, the frequency of use is increasing as various optical films including display-related display members.
  • polyester films are used as base films such as films and light condensing films for their excellent mechanical properties, dimensional stability and transparency.
  • a force using a thick film of 50 m or more is used.
  • adhesion to a hard coat layer, adhesion to a prism lens layer, adhesion to a lenticular lens layer, Adhesiveness with the light diffusion layer is required.
  • ultraviolet (UV) curable resin is often used for these layers, and adhesion to the layers is required.
  • the biaxially oriented polyester film surface generally has a high crystal orientation, so it has the disadvantage of poor adhesion to various paints, adhesives, inks, etc.
  • the processing step after forming the functional layer the processing step after forming the functional layer
  • problems such as peeling of the functional layer from the base film force occur during actual use. For this reason, methods for imparting easy adhesion to the polyester film surface by various methods have been studied.
  • a method of providing acrylic modified polyurethane as a primer layer on the film surface (Patent Document 1, Patent Document 2), A method of providing a copolyester as a primer layer (Patent Document 3), a method of providing a copolyester resin and an isocyanate cross-linking agent as a single layer (Patent Document 4, Patent Document 5, and Patent Document 6), A method of using a positive imide crosslinking agent as a primer layer (Patent Document 7) has been proposed.
  • a method of providing the primer layer by coating and imparting easy adhesion, in particular, applying a corona discharge treatment to the polyester film before the completion of crystal orientation as necessary to prepare a coating solution containing the resin component A method (in-line coating method) in which the crystal orientation is completed by applying, drying, stretching, and heat treatment is actively performed in the industry.
  • Patent Document 1 JP-A-6-346019 (Page 1, Claims)
  • Patent Document 2 JP 2000-229394 (first page, claims)
  • Patent Document 3 JP 2001-138465 A (page 1, claims)
  • Patent Document 4 Japanese Patent Laid-Open No. 9 11423 (Page 1, Claims)
  • Patent Document 5 Japanese Patent Laid-Open No. 2002-53687 (Page 1, Claims)
  • Patent Document 6 Japanese Unexamined Patent Publication No. 2003-49135 (Page 1, Claims)
  • Patent Document 7 Japanese Unexamined Patent Publication No. 2001-79994 (first page, claims)
  • adhesion imparting for example, a method of providing an acrylic-modified polyurethane as a primer layer on a film surface, a method of providing a copolyester as a primer layer, or the like may have insufficient adhesion to a UV curable resin.
  • a crosslinking agent is not used, problems such as wrinkles that do not provide any adhesiveness after storage (moisture and heat resistant adhesiveness) in a wet and heat environment are likely to occur.
  • a crosslinking agent positively, such as a method of providing a copolymerized polyester resin and an isocyanate cross-linking agent as a primer layer, or a method of using a calpositimide cross-linking agent as a primer layer as a cross-linking agent are described above. Adhesive improvement effect is recognized However, adhesion to UV curable resin, especially solvent-free UV curable resin constituting the prism lens layer, is still often insufficient.
  • the object of the present invention is to solve the above-mentioned drawbacks, not only the initial adhesiveness, but also excellent in heat-and-moisture resistance and adhesiveness after UV irradiation, and in transparency and coating appearance.
  • the object is to provide an extremely excellent laminated film.
  • the present invention also has the following constitutional power.
  • thermoplastic resin film On at least one side of the thermoplastic resin film,
  • a laminated film containing acrylic 'urethane copolymer resin (A), polyester resin (B), and crosslinker (C) is provided.
  • the crosslinking agent (C) is a strong isocyanate-based crosslinking agent and Z or a carpositimide-based crosslinking agent, and 100 parts by weight in total of the acrylic urethane copolymer resin (A) and the polyester resin resin (B).
  • Crosslinking agent (C) is a cross-linking of an isocyanate-based crosslinking agent and a carpositimide-based crosslinking agent.
  • the cross-linking agent (C) is a polymer type cross-linking agent (1) to (4),
  • the acrylic / urethane copolymer resin (A) and polyester resin (B) have a solids weight ratio of 95Z5 to 60Z40 (1) to (7)!
  • Crosslinking agent (C) is 10 to 40 parts by weight of isocyanate cross-linking agent for 100 parts by weight of acrylic urethane copolymer resin (100) and polyester resin ( ⁇ ).
  • Thermoplastic resin film strength A laminated film according to any one of (1) to (9), which is a polyethylene terephthalate film or a polyethylene 2,6 naphthalate film.
  • the laminated film of the present invention is excellent not only in the initial adhesiveness, but also particularly in wet heat resistance and adhesiveness after UV irradiation, and is extremely excellent in transparency and coated appearance.
  • thermoplastic resin film as used in the present invention is a general term for films that melt or soften by heat, and is not particularly limited, but representative examples include polyester films and polypropylene films.
  • Polyolefin film such as film and polyethylene film, polylactic acid film, polycarbonate film, polymethyl methacrylate film, acrylic film such as polystyrene film, polyamide film such as nylon, polychlorinated bull film, polyurethane film, fluorine It is possible to use a base film, a polyphenylene sulfide film, or the like.
  • These may be a homopolymer or a copolymer.
  • polyester films, polypropylene films, polyamide films, etc. are preferred in terms of mechanical properties, dimensional stability, transparency, and polyester films are particularly preferred in terms of mechanical strength and versatility. I like it.
  • the force for explaining the polyester film as a representative example of the laminated film of the present invention is not limited to this.
  • polyester is a general term for polymers having an ester bond as a main bond chain, and includes ethylene terephthalate, propylene terephthalate, ethylene 2 , 6 Naphthalate, Butylene terephthalate, Propylene 1, 2, 6 Naphthalate, Ethylene 1 ⁇ , ⁇ -Bis (2 chlorophenoxy) ethane-4,4'-dicarboxylate What is used as a component can be preferably used. These constituent components may be used alone or in combination of two or more.
  • polyester having ethylene terephthalate as a main constituent that is, polyethylene terephthalate is used. It is particularly preferable to use it.
  • polyethylene 2, 6 naphthalate having excellent heat resistance and rigidity is more preferable.
  • These polyesters may be further partially copolymerized with other dicarboxylic acid components and diol components, preferably 20 mol% or less.
  • additives such as an antioxidant, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, an organic lubricant, a pigment, a dye, organic or inorganic fine particles, a filler. Add anti-static agents, nucleating agents, etc. to the extent that they do not deteriorate their properties.
  • Intrinsic viscosity of the polyester described above is preferably in the range of 0.4 to 1.2 dlZg, more preferably in the range of 0.5 to 0.8 dlZg. Is suitable for carrying out the present invention.
  • the polyester film using the polyester is preferably biaxially oriented in a state where a laminated film is provided.
  • Biaxially oriented polyester film generally refers to an unstretched polyester sheet or film in the longitudinal direction and width direction. Each film is stretched about 2.5 to 5 times in the direction and then heat-treated to complete the crystal orientation, and shows a biaxial orientation pattern by wide-angle X-ray diffraction.
  • the thickness of the polyester film is not particularly limited, and is appropriately selected depending on the application and type in which the laminated film of the present invention is used. However, from the viewpoint of mechanical strength, handling properties, etc. Is preferably 1 to 500 ⁇ m, more preferably 5 to 250 ⁇ m, and most preferably 25 to 200 m.
  • the polyester film substrate may be a composite film by coextrusion. In particular, when a composite film of two or more layers is used, both smoothness and smoothness can be achieved while maintaining transparency, for example, by adding easy-to-slip fine particles to the skin layer and making the core layer non-particulate. It's easy to do.
  • the obtained film can be used by bonding it by various methods.
  • the laminated film refers to a film-like film that is formed in a laminated structure on the surface of a thermoplastic resin film as a substrate.
  • the film itself may be a single layer or a plurality of layers! /.
  • the laminated film of the laminated film of the present invention is a composition comprising an acrylic urethane copolymer resin (A), a polyester resin (B), and a crosslinking agent (C), and the crosslinking agent.
  • (C) is a composition which also has an isocyanate crosslinking agent and a Z or carpositimide crosslinking agent.
  • the above composition is preferably 50% by weight or more of the entire laminated film, more preferably 70% by weight or more, and most preferably 80% by weight or more.
  • a copolymer of acrylic and urethane is used from the viewpoint of adhesion and UV resistance (adhesion after UV irradiation).
  • the acrylic / urethane copolymerized resin (A) used for the laminated film of the laminated film of the present invention is not particularly limited as long as it is a resin obtained by copolymerizing an acrylic component and a urethane component.
  • Acrylic urethane copolymer resin having a core layer as the core layer is preferred. In this case, it is preferable that the core layer has a form in which the core layer is exposed in a state where the core layer is completely wrapped by the skin layer.
  • the core layer when the core layer is completely encased by the skin layer, when the resin is applied and dried to form a film, it becomes a surface state having only acrylic characteristics, and the characteristics of the urethane derived from the core layer It is possible to obtain a surface state having
  • the state where the core layer is not encased by the skin layer that is, the state where both are separated is simply A mixture of acrylic and urethane.
  • acrylics with low surface energy of the resin are selectively coordinated on the surface side.
  • Acrylic 'urethane copolymer resin having a core' skin structure is, for example, firstly subjected to first-stage emulsion polymerization using a monomer, an emulsifier, a polymerization initiator, and water that form a core portion of the polymer resin. After the polymerization is substantially completed, a monomer for forming the shell portion and a polymerization initiator are added, and the second emulsion polymerization can be performed. At this time, since the copolymerized resin produced has a two-layer structure, in the second stage emulsion polymerization, no emulsifier is added, or even if it is added, the amount is such that no new core is formed.
  • the amount of emulsifier charged during the second stage emulsion polymerization is adjusted.
  • a portion corresponding to the skin layer to be subjected to the second-stage emulsion polymerization is polymerized separately, and the second-stage emulsion polymerization is further carried out on the core surface.
  • the above-mentioned acrylic urethane copolymer resin (A) is prepared by, for example, copolymerizing an acrylic monomer constituting acryl in the presence of aqueous urethane, or by forming aqueous urethane and aqueous acrylic, particularly a crosslinkable functional group. It can be obtained by copolymerizing a water-based acrylic having water content, or by copolymerizing a water-based urethane and a water-based acrylic respectively with a crosslinkable functional group of each resin.
  • These water-based urethanes are functional groups that increase the affinity of ordinary urethane resin for water, such as carboxylic acid groups, sulfonate groups, sulfuric acid half ester bases and other functional groups, quaternary ammonia. Examples thereof include those having a cationic functional group such as a base introduced therein. Among these functional groups, anionic functional groups are preferred in view of dispersibility in water and reaction control during synthesis, and carboxylic acid groups and sulfonic acid groups are preferred.
  • the introduction of the carboxylic acid group is, for example, using a carboxylic acid group-containing polyhydroxy compound as one component of the polyhydroxy compound used as a raw material during urethane copolymerization, or a urethane having an unreacted isocyanate group.
  • a hydroxyl group-containing carboxylic acid amino group to the isocyanate group of The reaction can be carried out by reacting the contained carboxylic acid, adding the reaction product to an aqueous alkaline solution under high-speed stirring, and neutralizing.
  • introduction of a sulfonate group or a sulfate half ester base can be accomplished, for example, by generating a prepolymer from a polyhydroxy compound, a polyisocyanate and a chain extender, and reacting with a terminal isocyanate group or an amino group or a hydroxyl group.
  • a compound having sulfonate group or sulfate half ester base in the molecule and reacting and finally obtaining an aqueous urethane having sulfonate group or sulfate half ester base in the molecule.
  • a compound having a sulfonic acid group is used as one of raw materials to polymerize a urethane having a sulfonic acid group, and then the urethane is added to an alkaline aqueous solution with high-speed stirring to neutralize.
  • a sulfonic acid alkali salt for example, sulfone sodium base
  • an alkaline aqueous solution it is preferable to use an aqueous solution such as sodium hydroxide, potassium hydroxide, ammonia, and anolenoquinamine.
  • the alkali does not remain in the coating film after coating and drying. Amines that volatilize under solid conditions are particularly preferred. Carboxylate, sulfonate, amount of base, such as sulfuric acid half ester base 0. 5 X 10- 4 ⁇ 20 X 10- 4 equivalents Zg is preferably tool further 1 X 10- 4 ⁇ : LO X 10 — 4 equivalents Zg is preferred. If the proportion of the base is too small, the affinity of urethane for water is insufficient, making it difficult to prepare an aqueous dispersion, and if it is too large, the original properties of urethane are impaired, which is not preferable. Of course, the aqueous urethane forms a stable aqueous dispersion or forms an aqueous solution by using a dispersion aid as required.
  • base such as sulfuric acid half ester base 0. 5 X 10- 4 ⁇ 20 X 10- 4 equivalents Zg is preferably tool further 1 X 10- 4 ⁇ : LO X 10 — 4
  • polyhydroxy compounds used for the synthesis of urethane include polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, polytetramethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, and diethylene glycol.
  • Triethylene glycol poly force prolatathone, polyhexamethylene adipate, polyhexamethylene sebacate, polytetramethylene adipate, polytetramethylene sebacate, trimethylolpropane, trimethylololeethane, pentaerythritol Toll, glycerin and the like can be used.
  • poly-strength prolatatone it is preferable to use poly-strength prolatatone as the polyhydroxy compound.
  • the coating appearance is particularly excellent when coated on a film.
  • polyisocyanate compounds include hexamethylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate and An adduct of methylolpropane, an adduct of hexamethylene diisocyanate and trimethylolethane can be used.
  • carboxylic acid-containing polyol for example, dimethylolpropionic acid, dimethylolbutyric acid, dimethylol monovaleric acid, trimellitic acid bis (ethylene glycol) ester, and the like can be used.
  • amino group-containing carboxylic acid for example, j8-aminopropionic acid, y-aminobutyric acid, P-aminobenzoic acid and the like can be used.
  • hydroxyl group-containing carboxylic acid examples include 3-hydroxypropionic acid, ⁇ -hydroxybutyric acid, ⁇ - (2-hydroxyethyl) benzoic acid, malic acid, and the like.
  • Examples of the compound having an amino group or a hydroxyl group and a sulfone group include aminomethanesulfonic acid, 2-aminoethanesulfonic acid, 2-amino-5-methylbenzene-1-sulfonic acid, sodium ⁇ -hydroxyethanesulfonate, fatty acid, and the like.
  • Propansaltone and butanesultone addition products of aliphatic diprimary amine compounds can be used, and propanesultone addition products of aliphatic diprimary amine compounds are preferred.
  • examples of the compound containing an amino group or a hydroxyl group and a sulfuric acid half ester include, for example, aminoethanol sulfate, ethylenediamineethanol sulfate, aminobutanol sulfate, hydroxyethanol sulfate, ⁇ ⁇ ⁇ ⁇ ⁇ -hydroxypropanol sulfate, ⁇ -hydroxy Butanol sulfate can be used.
  • the acrylic monomer used in the acrylic urethane copolymer resin ( ⁇ ) used in the present invention is, for example, an alkyl acrylate (the alkyl group is methyl, ethyl, ⁇ -propyl).
  • alkyl methacrylate alkyl groups include methyl, ethyl, n-propyl, n-butyl, isobutyl, t-butyl, 2-ethyl hexyl, cyclohexyl, etc.
  • alkyl groups include methyl, ethyl, n-propyl, n-butyl, isobutyl, t-butyl, 2-ethyl hexyl, cyclohexyl, etc.
  • copolymerization of N-methylolacrylamide is particularly preferable in terms of improving self-crosslinkability and crosslinking density.
  • the copolymerization ratio of N-methylolacrylamide is preferably 0.5 to 5% by weight from the viewpoint of copolymerizability and the degree of cross-linking, and is more preferably 1 to 3% by weight in view of the coating appearance.
  • the moisture-resistant adhesion tends to be inferior
  • the stability of the aqueous dispersion of the resin tends to be inferior or the appearance of the coating tends to be deteriorated.
  • Examples of the other monomer include glycidyl group-containing monomers such as allyl glycidyl ether, sulfonic acid groups such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, etc.) or the like.
  • an acid anhydride group such as itaconic anhydride, butyl isocyanate, allylic isocyanate, styrene, vinyl methyl
  • the proportion of acrylic monomers in all monomers is 50 wt% or more, more preferably 70 wt% or more I prefer to be
  • the glass transition temperature (Tg) of the acrylic resin constituting the acrylic / urethane copolymer resin (A) is preferably 20 ° C or higher, more preferably 40 ° C or higher.
  • this glass transition temperature is less than 20 ° C., the heat resistance is insufficient, and for example, there is a tendency to block easily even at room temperature.
  • the ratio of "acrylic resin Z urethane" in the acrylic 'urethane copolymer resin (A) is preferably from “10Z90" to "70Z30", more preferably from “20 to 80" in weight ratio. “50 ⁇ 50”.
  • the ratio of acrylic resin is less than 10Z90, the adhesiveness after UV deterioration of the laminated film obtained after coating and drying tends to deteriorate, and when it exceeds 70-30, the surface of the laminated film is covered with acrylic. Since the ratio increases, the initial adhesion tends to deteriorate.
  • the weight ratio of acrylic resin / urethane / urethane can be adjusted to a desired value by adjusting the blending amount of the raw materials at the time of production of the acrylic / urethane copolymer resin (resin).
  • a method for producing an acrylic urethane copolymer resin (wax) includes, for example, adding a small amount of a dispersant and a polymerization initiator to the aqueous dispersion of the aqueous urethane described above, and maintaining the temperature at a constant temperature. The monomer is gradually added while stirring, and then the temperature is raised as necessary, and the reaction is continued for a certain period of time to complete the polymerization of the acrylic monomer to obtain an aqueous dispersion of acrylic / urethane copolymer resin.
  • a dispersant and a polymerization initiator to the aqueous dispersion of the aqueous urethane described above, and maintaining the temperature at a constant temperature.
  • the monomer is gradually added while stirring, and then the temperature is raised as necessary, and the reaction is continued for a certain period of time to complete the polymerization of the acrylic monomer to obtain an aqueous dispersion of acrylic / urethane copolymer resin
  • the polyester resin (wax) that can be used for the laminated film of the laminated film of the present invention has an ester bond in the main chain or side chain, and is obtained by polycondensation of a dicarboxylic acid and a diol. It is.
  • carboxylic acid component constituting the polyester resin
  • aromatic, aliphatic, and alicyclic dicarboxylic acids and trivalent or higher polyvalent carboxylic acids can be used.
  • Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, phthalate Acid, 2,5 dimethyl terephthalic acid, 1,4 naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, 2, 6 naphthalene dicarboxylic acid, 1, 2 bisphenoloxytane p, p Dandicarboxylic acid or the like can be used.
  • these aromatic dicarboxylic acid powers are preferably polyesters that occupy 30 mol% or more, more preferably 35 mol% or more, and most preferably 40 mol% or more of the total dicarboxylic acid component. It is preferable to use it.
  • Aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, dimer acid, 1,3 cyclopentanedicarboxylic acid, 1,2 cyclohexanone.
  • Xanthodicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like, and ester-forming derivatives thereof can be used.
  • the darikole component of polyester resin includes ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3 propanediol, 1,3 butanediol, 1,4 butanediol, 1,5 penta Njioru, 1, hexanediol to 6, 1, 7 heptane diol, 1, 8 Okutanji ol, 1, 9-1-nonanediol, 1, 10-decanediol, 2, 4-dimethyl-2 hexane 1 to E chill, 3 Jioru, neopentyl glycol, 2-Ethyl-2-butyl 1,3 propanediol, 2-ethyl-2-isobutyl-1,3 propanediol, 3-methyl-1,5-pentanediol, 2,2,4 trimethyl-1,6 hexanediol, 1,2 cycloto Xanthanimethanol, 1,3
  • polyester resin When the polyester resin is used as a coating solution in an aqueous solution, a compound containing a sulfonate group or a carboxylate group is used in order to facilitate water-solubility or water dispersion of the polyester resin.
  • U preferred to copolymerize compounds containing.
  • Examples of the compound containing a carboxylate group include trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexene mono-1,2,3tricarboxylic acid, trimesic acid, 1 , 2, 3, 4 Butanetetracarboxylic acid, 1, 2, 3, 4 Pentanetetracarboxylic acid, 3, 3 ', 4, 4, Monobenzophenone tetracarboxylic acid, 5- (2,5 dioxotetrahydrofurfuryl) 1-Methyl 3 cyclohexene mono 1,2 dicarboxylic acid, 5- (2,5-dioxotetrahydrofurfuryl) 3 cyclohexene mono 1,2 dicarboxylic acid, cyclopentane tetracarboxylic acid, 2, 3, 6, 7 Naphthalenetetracarboxylic acid, 1, 2, 5, 6 Naphthalenetetracarboxylic acid,
  • the copolymerization ratio in which trimellitic acid is used and a carboxyl group is preferably introduced into the side chain is not particularly limited, but 5 to 30 mol% is more preferable, and 5 to 20 is more preferable. Mol%. By setting it within this range, excellent effects are exhibited in terms of cross-linking with other cross-linking agents not only in terms of water dispersion of polyester resin, but also in suppressing hydrolysis resistance.
  • Examples of the compound containing a sulfonate group include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4 sulfonaphthalene 2,7 dicarboxylic acid, sulfo-p-xylylene glycol, 2-sulfo 1,4 bis (hydroxyethoxy) benzen and the like, or alkali metal salts, alkaline earth metal salts, and ammonium salts thereof can be used, but are not limited thereto.
  • the polyester resin is selected from terephthalic acid, isophthalic acid, sebacic acid, 5-sodium sulfoisophthalic acid as the acid component, and ethylene glycol, diethylene glycol, 1,4 butanediol as the glycol component. And a copolymer using a component selected from neopentyl glycol.
  • a copolymer containing trimellitic acid as its copolymer component can be suitably used instead of 5-sodium sulfoisophthalic acid.
  • the polyester resin used in the laminated film can be produced by the following production method.
  • terephthalate I will explain polyester resin using acid, isophthalic acid, 5-sodiumsulfoisophthalic acid, ethylene glycol and neopentyldaricol as glycol components.
  • Terephthalic acid isophthalic acid, the ability to directly esterify 5-sodium sulfoisophthalic acid with ethylene glycol, neopentyl dallicol, terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid and ethylene glycol, neopentyl glyco It can be produced by a method of producing by a first stage process of transesterifying the first product and a second stage process of polycondensation reaction of the reaction product of the first stage.
  • reaction catalyst for example, alkali metal, alkaline earth metal, manganese, cobalt, zinc, antimony, germanium, titanium compound, or the like can be used.
  • the intrinsic viscosity of the polyester resin used in the laminated film according to the present invention is not particularly limited, but is preferably 0.3 dlZg or more, more preferably 0.3 in terms of adhesiveness. It is 5 dlZg or more, most preferably 0.4 dlZg or more.
  • the glass transition point (hereinafter abbreviated as “Tg”) of the polyester resin is preferably 0 to 130 ° C., more preferably 10 to 85 ° C. If the Tg is less than 0 ° C, for example, the heat-resistant adhesiveness is inferior, or a blocking phenomenon occurs in which the laminated film adheres.On the other hand, if it exceeds 130 ° C, the stability and water dispersibility of the resin are low. Since it may be inferior, it is not preferable.
  • acrylic resin in addition to the above-mentioned acrylic / urethane copolymer resin (A) and polyester resin (B), acrylic resin, polyester resin (B) Different types of polyester and urethane resins may be used in combination. Three or more types may be used in combination.
  • an isocyanate cross-linking agent that can be used in the laminated film of the laminated film of the present invention
  • Adduct of sulfonate and hexanetriol Adduct of sulfonate and hexanetriol, adduct of tolylene diisocyanate and trimethylolpropane
  • Diisocyanate isophorone diisocyanate, 1,5 naphthalene diisocyanate, 3, 3, -bitolylene 4,4 'diisocyanate, 3, 3' di
  • a polymer type isocyanate cross-linking agent having a plurality of isocyanate groups at the end or side chain of a polymer such as polyester resin or acrylic resin makes the laminated film flexible and tough. It can be preferably used.
  • the isocyanate group is masked with a blocking agent in view of the pot life of the coating agent in which the isocyanate group easily reacts with the water.
  • the block isocyanate compound etc. which were made can be used suitably.
  • a typical system for the blocking agent is a system in which the blocking agent is volatilized by heating after the application and heat of the drying process to expose the isocyanate group and cause a crosslinking reaction.
  • the isocyanate group may be a monofunctional type or a polyfunctional type, but a polyfunctional type block polyisocyanate-based compound can be preferably used in that the crosslinking density can be easily increased.
  • block polyisocyanate compound a low-molecular or high-molecular compound having two or more block isocyanate groups represented by the following general formula (I) can be used.
  • the block isocyanate group represented by [] in the formula (I) is decomposed into an isocyanate group represented by the following formula (II) by heating, and this isocyanate group activates other resin components constituting the laminated film.
  • the active hydrogen is a hydrogen element contained in a hydroxyl group (one OH), a carboxyl group (one COOH), or the like.
  • R 1 is an aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms.
  • R 2 and R 3 are each an aliphatic hydrocarbon group having 1 to 7 carbon atoms or a sulfinate group (one SO M
  • M is an alkali metal
  • R 4 in the formula (I 3) R 5 is hydrogen element or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, R 4 to R 5 may be a lactam ring bonded thereto.
  • R 6, R 7, R 8 are hydrogen element or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, alicyclic hydrocarbon group or an aromatic hydrocarbon radical, R 6 to R 7 may be a cyclic mercaptan ring bonded thereto.
  • R 9 , R 10 and R 11 are hydrogen elements, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a group represented by OR 12 (R 12 is a group having 1 to 5 carbon atoms) 4 aliphatic hydrocarbon groups).
  • Examples of the low-molecular or high-molecular compound having two or more block isocyanate groups described above include diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, and trimethylol.
  • a carpositimide-based crosslinking agent that can be used in the laminated film of the laminated film of the present invention Is not particularly limited as long as it has at least one calpositimide structure represented by the following general formula (1) per molecule, but two or more per molecule in terms of moisture and heat resistance
  • a polycarposimide-based cross-linking agent having the use of a polymer type isocyanate cross-linking agent having a plurality of carpositimide groups at the end or side chain of a polymer such as polyester resin or acrylic resin makes the laminated film flexible and tough. It can be preferably used.
  • a known technique can be applied to the production of the polycarbopositimide-based crosslinking agent.
  • the method described in Japanese Patent Publication No. 47-33279 and Japanese Patent Application Laid-Open No. 09-235508 can be used. It can be obtained by polycondensation of a diisocyanate compound in the presence of a catalyst.
  • the diisocyanate compound which is a starting material of the polycarposimide-based crosslinking agent aromatic, aliphatic, alicyclic diisocyanate and the like can be used, and specifically, tolylene diisocyanate.
  • xylene diisocyanate diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, etc.
  • a surfactant polyalkylene oxide
  • Hydrophilic monomers such as quaternary ammonium salts of amino alcohols and hydroxyalkyl sulfonates may also be used as additives.
  • crosslinking agent (C) an isocyanate crosslinking agent and a Z or carpositimide crosslinking agent are used.
  • crosslinking agent for example, Melamine-based crosslinking agent, epoxy-based crosslinking agent, aziridine-based crosslinking agent, amide epoxy compound, titanate-based coupling agent such as titanium chelate, oxazoline-based crosslinking agent, isocyanate-based crosslinking agent, methylolation or alkylolization Urea and acrylic amides can also be used.
  • the laminated film of the laminated film of the present invention has an “acrylic / urethane copolymerized resin (A) Z polyester resin (B)” force ⁇ 95 / 5] to a solid content weight ratio in the laminated film.
  • “60Z40” is more preferable in terms of adhesiveness, especially adhesiveness after UV irradiation, and more preferably “90ZlO” to “60 / 40J, most preferably "80Z20" to "70/30".
  • the laminated film of the laminated film of the present invention has a solid weight ratio of 100% by weight in total of acrylic urethane copolymer resin ( ⁇ ) and polyester resin resin ( ⁇ ).
  • the crosslinking agent (C) must have a power of 70 parts by weight. When the added amount of the crosslinking agent (C) is less than 5 parts by weight or more than 70 parts by weight, the heat-and-moisture resistance and the adhesion after UV irradiation are deteriorated.
  • the amount of the crosslinking agent (C) added is preferably 15 to 70 parts by weight, more preferably 25 to 45 parts by weight. When this amount is added, the adhesion, moisture-proof adhesion, adhesion after UV irradiation, and coating appearance are very good.
  • the crosslinking agent (C) is an isocyanate crosslinking agent and a cocoon or carboimide crosslinking agent, and the combined amount of both is particularly preferred as described above.
  • the isocyanate crosslinking agent is more preferably 15 to 30 parts by weight
  • the carpositimide crosslinking agent is more preferably 5 to 20 parts by weight.
  • the calpositimide cross-linking agent is 5 to 20 parts by weight, most preferably 10 to 20 parts by weight, a laminated film having excellent transparency in addition to the above-described adhesiveness can be obtained.
  • additives such as an antioxidant, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, an organic lubricant, and a pigment are included in the laminated film within the range in which the effects of the present invention are not impaired.
  • Dyes, organic or inorganic fine particles, fillers, antistatic agents, nucleating agents, and the like may be blended.
  • inorganic particles to be added typically, silica, colloidal silica, alumina, alumina sol, kaolin, talc, My strength, calcium carbonate, or the like can be used.
  • the inorganic particles used may be in a range that does not impair the effects of the present invention.
  • Particles added to the laminated film preferably have an average particle size of 0.005-0.3 / zm, more preferably 0.02 to 0.15 m, and most preferably 0.04.
  • the blending ratio is not particularly limited, but is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight.
  • the haze of the laminated film is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less.
  • the laminated film becomes turbid, for example, the display becomes cloudy or the resolution is lowered.
  • the above haze is not particularly limited and can be used.
  • the water-based resin coating method may be, for example, a reverse coating method, a spray coating method, a bar coating method, a gravure coating method, a rod coating method, a die coating method, or the like.
  • the thickness of the laminated film is not particularly limited, but usually it is preferably in the range of 0.005-0. 2 ⁇ m, more preferably 0.00 to 0.1 m, and most preferably 0.75. The range is from 0.01 ⁇ m to 0.08 ⁇ m. If the thickness of the laminated film is too thin, adhesion failure may occur.
  • the preferred method for providing the laminated film is the method of applying the polyester film during the production process and stretching it together with the base film.
  • a melt-extruded polyester film before crystal orientation is stretched about 2.5 to 5 times in the longitudinal direction, and the coating solution is continuously applied to a uniaxially stretched film.
  • the coated film is dried while passing through a zone heated in stages, and stretched about 2.5 to 5 times in the width direction.
  • it can be obtained by a method (inline coating method) in which the crystal orientation is completed by being continuously guided to a heating zone of 150 to 250 ° C.
  • the coating solution used in this case is preferably water-based in terms of environmental pollution and explosion-proof properties.
  • a simultaneous biaxial stretching method in which a coating solution is continuously applied on an unstretched film and stretched in the vertical and horizontal directions can also be adopted.
  • the film is scratched because there is little contact with the roll. It is an advantageous method, such as a short time.
  • the surface of the base film (in the case of the above example, a uniaxially stretched film or an unstretched film) is subjected to a corona discharge treatment, etc.
  • Force to make the wetting tension preferably 47mNZm or more, more preferably 50mNZm or more Since the adhesiveness of the membrane to the base film can be improved, it can be preferably used. Further, it is preferable to improve the adhesion to the substrate film by adding a slight amount of an organic solvent such as isopropyl alcohol, butylcetone sorb, N-methyl-2-pyrrolidone in the coating liquid.
  • PET polyethylene terephthalate
  • PET pellets After 5 to 0.8 dlZg of PET pellets are vacuum-dried, they are fed to an extruder, melted at 260-300 ° C, extruded into a sheet from a T-shaped die, and the surface temperature is 10 using an electrostatic application casting method. It is wound around a mirror casting drum of ⁇ 60 ° C. and cooled and solidified to produce an unstretched PET film. This unstretched film is stretched 2.5 to 5 times in the machine direction (film traveling direction) between rolls heated to 70 to 120 ° C.
  • At least one surface of the film is subjected to corona discharge treatment, the surface has a wetting tension of 47 mNZm or more, and an aqueous coating solution that is effective in the present invention is applied to the treated surface.
  • the coated film is gripped with a clip, guided to a hot air zone heated to 70 to 150 ° C, dried, stretched 2.5 to 5 times in the width direction, and subsequently heat treated zone of 160 to 250 ° C And heat treatment for 1 to 30 seconds to complete crystal orientation.
  • a relaxation treatment of 1 to 10% may be performed in the width direction or the longitudinal direction as necessary.
  • Biaxial stretching may be either longitudinal, transverse sequential stretching, or simultaneous biaxial stretching, and may be re-stretched in either the longitudinal or transverse direction after longitudinal and transverse stretching.
  • the thickness of the polyester film is not particularly limited, but 1 to 500 / ⁇ ⁇ is preferable.
  • the base film on which the laminated film is provided contains at least one substance selected from the laminated film-forming composition or the reaction product of the laminated film-forming composition, so that the laminated film and the base film are contained. Adhesiveness with a material film can be improved, and easy slipperiness can be improved.
  • the added amount of the laminated film forming composition or these reaction products is preferably from 0.0005 wt% to less than 20 wt% in terms of strength, adhesiveness and slipperiness. In particular, considering environmental protection and productivity, recycled pellets containing the laminated film forming composition The method used is preferred.
  • the laminated film of the present invention thus obtained has not only initial adhesiveness, but also excellent heat and moisture resistance, adhesiveness after UV irradiation, and excellent transparency. It can be suitably used for easy adhesive films for optical use for displays such as liquid crystal televisions, plasma display televisions, rear projection televisions, and easy adhesive films having excellent adhesion to various coatings.
  • the characteristic measurement method and effect evaluation method in the present invention are as follows.
  • ink A UV curable ink
  • ink B oxidative polymerization ink
  • ink C organic solvent paint UV curable hard coating agent
  • ink D A type of resin (ink D) was used (the following 4 types of ink).
  • Ink A "Best Cure I" 161 Black (T & K Toka Co., Ltd.)
  • Ink B HS ink (HS—OS) manufactured by Kuboti Ink Co., Ltd.
  • Ink C Hard coating agent (adjusted with the following composition ratio) 'Dipentaerythritol hexaatalylate: 70 parts by weight
  • ink A the ink was applied to a thickness of about 1.5 ⁇ m on the laminated film by roll coating. Thereafter, UV irradiation was performed using an ultraviolet lamp with an irradiation intensity of 120 WZcm at an irradiation distance (distance between the lamp and the ink surface) of 12 cm, a conveyor speed of 6 mZ, and an integrated intensity of about 200 mjZcm 2 to cure the ultraviolet curable ink. Adhesion evaluation was performed by the following method.
  • ink B the ink was applied to a thickness of about 1.5 ⁇ m on the laminated film by roll coating. Thereafter, it was left to stand for 24 hours to be cured.
  • the adhesion evaluation was performed by the method described above.
  • ink C For ink C, apply a bar coater so that the film thickness after curing is 5 m, and then use an ultraviolet lamp with an irradiation intensity of 120 WZcm, and the irradiation distance (distance between the lamp and the ink surface) The hard coat layer was cured by UV irradiation at 12 cm, a conveyor speed of 2 mZ, and an integrated intensity of about 550 mjZcm 2 . In addition, adhesive evaluation was performed by the above-mentioned method.
  • Ink D was applied to a thickness of about 25 ⁇ m by the wire bar coating method, and then an ultraviolet lamp with an irradiation intensity of 120 WZcm was used, the irradiation distance (distance between the lamp and the ink surface) was 12 cm, and the conveyor speed UV irradiation was performed at an integrated intensity of about 550 mjZcm 2 for 2 mZ to cure the solventless transparent UV curable resin.
  • adhesive evaluation was performed by the above-mentioned method.
  • ink D in (2) above Before applying ink D in (2) above, the adhesive evaluation is performed in the same manner except that after the UV irradiation is applied to the laminated film surface of the laminated film under the same conditions as the curing conditions after application, ink D is applied. went.
  • haze and total light transmittance were used as an index of transparency.
  • a normal condition 23 ° C, relative humidity 65%
  • the laminated film was allowed to stand for 2 hours, and then fully automated direct reading haze computer “HGM-2DP” manufactured by Suga Test Instruments Co., Ltd. V.
  • the average value measured three times was used as the haze value of the sample.
  • Measurement was performed by connecting an SSC5200 disk station manufactured by Seiko Denshi Kogyo Co., Ltd. to a DSC (differential scanning calorimeter) RDC220 manufactured by Seiko Electronics Co., Ltd.
  • the DSC measurement conditions are as follows. That is, after adjusting the sample lOmg to an aluminum pan, place it in the DSC device (reference: the same type of aluminum pan without sample), heat at 300 ° C for 5 minutes, and then use in liquid nitrogen Rapid cooling treatment. The sample is heated at 10 ° CZ and the glass transition point (Tg) is detected from the DSC chart. As the glass transition temperature (Tg), the midpoint glass transition temperature (Tmg) of ISO IS7121—1987 is adopted.
  • the coated surface of the laminated film of the present invention was inspected for coating by the following method using a three-wavelength fluorescent lamp as a light source in a dark room. If the rating is "3" or higher, it is judged that it can be used. Note that unevenness of the coating layer is caused by irregular stripes due to slight differences in the coating thickness of the coating layer, and this is inspected as “unevenness”. Especially with reflected light rather than inspection with transmitted light. This method was adopted because the inspection looks clearer.
  • PET pellets (extrinsic viscosity 0.63dl / g) that do not contain external particles are sufficiently vacuum-dried, then fed to an extruder and melted at a temperature of 285 ° C, extruded into a T-shaped die force sheet, It was wound around a mirror casting drum having a surface temperature of 25 ° C. by using an electrostatic application casting method and cooled and solidified.
  • the unstretched film thus obtained was heated to a temperature of 88 ° C. and stretched 3.3 times in the longitudinal direction to obtain a uniaxially stretched film.
  • the uniaxially stretched film was subjected to corona discharge treatment in air, and the following laminated film forming coating solution was applied to the treated surface.
  • the uniaxially stretched film coated with the film-forming coating liquid is guided to the preheating zone while being held with a clip, dried at a temperature of 95 ° C, and then continuously in the width direction at a heating zone of 110 ° C. 3.
  • the film was stretched 4 times and further heat-treated in a heating zone at a temperature of 235 ° C to obtain a laminated PET film having a crystal orientation completed.
  • the thickness of the obtained PET film was 100 ⁇ m, and the thickness of the laminated film was 0.07 m.
  • Table 1 It had excellent transparency such as haze and total light transmittance, as well as excellent adhesion, heat and moisture resistance, and adhesion after UV irradiation.
  • Acrylic-urethane copolymer resin-based aqueous dispersion (Sannaron WG-353 (prototype) manufactured by Shannan Synthetic Chemical Co., Ltd.).
  • the solid weight ratio of acrylic resin component Z urethane resin component is 12Z23, and 2 parts by weight of triethylamine is used as an aqueous dispersion.
  • polyester resin glass transition temperature: 38 ° C
  • Block isocyanate aqueous dispersion (“Elastoron” E- 37 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • Coating liquid Al, coating liquid Bl, and coating liquid C1 were the same as in Example 1.
  • the coating liquid for forming the laminated film was used.
  • Example 2 The following laminated film forming coating liquid was used instead of the laminated film forming coating liquid used in Example 1.
  • a laminated PET film was obtained in the same manner as in Example 1 except for the above.
  • Coating liquid Al, coating liquid Bl, and coating liquid C1 were the same as in Example 1.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • Ammonium salt type aqueous dispersion of polyester resin (glass transition temperature: 37 ° C) comprising the following copolymer composition.
  • Table 1 It had excellent transparency such as haze and total light transmittance, as well as excellent adhesion, wet heat resistance, and adhesion after UV irradiation.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • Polymerization was carried out on 90 parts by weight of an aqueous dispersion of carboxyl group-containing water-based polyurethane ("Hydran" AP-40, manufactured by Dainippon Ink & Chemicals, Inc.) further diluted with water to 10% by weight. Dissolve 0.1 parts by weight of azoisopetiti-tolyl as an initiator, and add the following ateryl monomer (finally adjust the solid weight ratio of acrylic resin component Z urethane resin component to 50Z50), A polymerization reaction was performed at a temperature of 80 to 82 ° C. for 2 hours to obtain an aqueous dispersion of an acrylic / urethane copolymer resin.
  • Hydran carboxyl group-containing water-based polyurethane
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • a coating solution for forming a laminated film was prepared by mixing 10 parts by weight.
  • Table 1 It was excellent in haze and total light transmittance, and extremely excellent in adhesion, wet heat resistance, and adhesion after UV irradiation.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • a coating solution for forming a laminated film was prepared by mixing 10 parts by weight.
  • Table 1 It was extremely excellent in haze and total light transmittance, and very excellent in adhesion, wet heat resistance, and adhesion after UV irradiation.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • Ammonium salt type aqueous dispersion of polyester resin (glass transition temperature: 20 ° C) comprising the following copolymer composition.
  • Example 1 'The same coating liquid C1 as in Example 1 was used.
  • a coating solution for forming a laminated film was prepared by mixing 10 parts by weight.
  • Table 1 It was extremely excellent in haze and total light transmittance, and very excellent in adhesion, wet heat resistance, and adhesion after UV irradiation.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • 'Coating solution C2 was the same as in Example 4.
  • a coating solution for forming a laminated film was prepared by mixing 10 parts by weight.
  • Table 1 It was extremely excellent in haze and total light transmittance, and had excellent adhesion, heat-and-moisture resistance, and adhesion after UV irradiation.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • 30 parts by weight of coating liquid C3 and coating liquid C2 A coating solution for forming a laminated film was prepared by mixing 10 parts by weight.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • Aqueous solution of polyvalent carpositimide ("Carposide Ride 'V-02", Carposiimide equivalent 590 manufactured by Nisshinbo Co., Ltd.)
  • the above coating liquid A1 and coating liquid B2 in solid weight ratio, coating liquid A1Z coating liquid B2 9 OZlO
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • a colloidal silica aqueous coating solution with an average particle size of 80 nm (“Catalyst Kogyo Co., Ltd.,“ Power Taloid, SI-80P ”).
  • Table 1 It was extremely excellent in haze and total light transmittance, and very excellent in adhesiveness, heat-and-moisture resistance, and adhesiveness after UV irradiation.
  • PET pellets used in Example 9 PET pellets containing 0.2% by weight of colloidal silica having an average particle size of 1.5 / zm (extreme viscosity 0.63 dlZg) were used.
  • a laminated PET film was obtained in the same manner as in Example 9 except that it was used.
  • Example 9 'Coating solution Al, coating solution B2, coating solution Cl, and coating solution C2 were the same as in Example 9.
  • a mixed liquid for forming a laminated film was prepared by mixing 10 parts by weight of the coating liquid C2.
  • Table 1 It was extremely excellent in adhesion, wet heat resistance, and adhesion after UV irradiation. Since it has a high haze with a high total light transmittance, it can be suitably used for, for example, a light diffusion film.
  • PET pellets (extreme viscosity 0.60 dl / g) containing 10% by weight of polymethylpentene were sufficiently vacuum-dried and then fed to Extruder A heated to 280 ° C. Also, PET pellets (intrinsic viscosity 0.63 dlZg) containing 0.002% by weight of colloidal silica with an average particle size of 1.5 m are sufficiently vacuum-dried and then supplied to Extruder B heated to 285 ° C. did .
  • Polymer extruded from extruders A and B are laminated by coextrusion to form a three-layer structure of BZAZB, extruded into a sheet form from a T-shaped die, and surface temperature of 25 ° using the electrostatic application casting method
  • the film was wound around a C mirror casting drum and cooled and solidified to obtain an unstretched film.
  • the unstretched film thus obtained was heated to 90 ° C and stretched 3.2 times in the longitudinal direction to obtain a uniaxially stretched film.
  • the uniaxially stretched film was subjected to corona discharge treatment in the air, and the following laminated film forming coating solution was applied to the treated surface.
  • the uniaxially stretched film on which the coating solution for forming the laminated film is applied is guided to the preheating zone while being gripped with a clip, dried at a temperature of 95 ° C, and then continuously in the heating zone at a temperature of 110 ° C in the width direction.
  • the film was stretched 3 times and further subjected to heat treatment in a heating zone at a temperature of 210 ° C to obtain a laminated PET film in which crystal orientation was completed.
  • the coating liquid C1 is 25 parts by weight with respect to 100 parts by weight.
  • a mixed liquid for forming a laminated film was prepared by mixing 10 parts by weight of C2. At this time, the solid content weight ratio of each coating liquid is the coating liquid A1Z.
  • Coating solution B2Z coating solution ClZ coating solution C2 70Z30Z25Z10.
  • Table 1 It was extremely excellent in adhesion, wet heat resistance, and adhesion after UV irradiation. Since it has a high haze with a high total light transmittance, it can be suitably used for, for example, a light diffusion film.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • Example 2 The following laminated film forming coating liquid was used instead of the laminated film forming coating liquid used in Example 1.
  • a laminated PET film was obtained in the same manner as in Example 1 except for the above.
  • a coating solution for forming a laminated film was prepared by mixing 10 parts by weight of C2.
  • Table 1 Adhesion, heat-and-moisture resistance, and adhesion after UV irradiation were poor.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • Mixed A laminated film forming coating solution was obtained.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • the coating liquid was used.
  • Table 1 Adhesion, heat-and-moisture resistance, and adhesion after UV irradiation were poor.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • the coating liquid for forming the laminated film was used.
  • Table 1 It was inferior in moisture and heat resistance and adhesion after UV irradiation.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • a coating solution for forming a laminated film was used.
  • Table 1 It was inferior in wet heat resistance and adhesion after UV irradiation.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • Polyurethane Pro-Lataton as the polyol component and Hexamethylene diisocyanate as the diisocyanate component were used to create a polyurethane water dispersion having a poly-strength prolatatone skeleton, and water was added to dilute it to 10% by weight.
  • a polymerization reaction at a temperature of 80 to 82 ° C. for 2 hours to obtain a water dispersion of an acrylic / urethane copolymer resin.
  • a coating solution for forming a laminated film was prepared by mixing 10 parts by weight.
  • Table 2 It was extremely excellent in haze and total light transmittance, and extremely excellent in adhesiveness, heat-and-moisture resistance, adhesion after UV irradiation, and coating appearance.
  • Example 2 The following laminated film forming coating liquid was used instead of the laminated film forming coating liquid used in Example 1.
  • a laminated PET film was obtained in the same manner as in Example 1 except for the above.
  • a coating solution for forming a laminated film was prepared by mixing 10 parts by weight.
  • Table 2 It was extremely excellent in haze and total light transmittance, and extremely excellent in adhesiveness, heat-and-moisture resistance, adhesion after UV irradiation, and coating appearance.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • Example 18 'The same coating liquid A4 as in Example 18 was used.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.
  • a laminated PET film was obtained in the same manner as in Example 1 except that the following laminated film forming coating solution was used instead of the laminated film forming coating solution used in Example 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Le problème à résoudre dans le cadre de la présente invention consiste à fournir un film stratifié qui est excellent en termes d’adhérence initiale, d'adhérence après un vieillissement par chauffage en milieu humide et d'adhérence après une irradiation avec des rayons UV, et est également excellent en termes de transparence et d’aspect de revêtement. La solution proposée est un film stratifié comprenant un film de résine thermoplastique et un film stratifié disposé sur au moins un côté du film de résine thermoplastique, le film stratifié comprenant une résine de copolymère acrylique/uréthane (A), une résine de polyester (B) et un agent de réticulation (C), l'agent de réticulation (C) étant un agent de réticulation de type isocyanate et/ou un agent de réticulation de type carbodiimide et contenu en une quantité de 5 à 70 parties en poids sur la base de 100 parties en poids de la somme de la résine de copolymère acrylique/uréthane (A) et de la résine de polyester (B).
PCT/JP2006/317951 2005-09-12 2006-09-11 Film stratifié Ceased WO2007032295A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
KR1020087008709A KR101244471B1 (ko) 2005-09-12 2006-09-11 적층 필름
CN2006800412378A CN101300294B (zh) 2005-09-12 2006-09-11 层合薄膜
US11/991,836 US7972700B2 (en) 2005-09-12 2006-09-11 Laminated film
EP20060797777 EP1942132B1 (fr) 2005-09-12 2006-09-11 Film stratifié
JP2006529407A JP4973187B2 (ja) 2005-09-12 2006-09-11 積層フィルムおよび積層フィルムの製造方法

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JP2005263422 2005-09-12
JP2005-263422 2005-09-12

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WO2007032295A1 true WO2007032295A1 (fr) 2007-03-22

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US (1) US7972700B2 (fr)
EP (1) EP1942132B1 (fr)
JP (1) JP4973187B2 (fr)
KR (1) KR101244471B1 (fr)
CN (1) CN101300294B (fr)
AT (1) ATE523549T1 (fr)
TW (1) TWI406762B (fr)
WO (1) WO2007032295A1 (fr)

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WO2011162045A1 (fr) * 2010-06-22 2011-12-29 三菱樹脂株式会社 Film polyester stratifié
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JP2013001099A (ja) * 2011-06-22 2013-01-07 Mitsubishi Plastics Inc 積層ポリエステルフィルム
JP2014088042A (ja) * 2014-02-03 2014-05-15 Mitsubishi Plastics Inc 積層ポリエステルフィルム
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JP2014159176A (ja) * 2011-03-09 2014-09-04 Toyobo Co Ltd 易接着性ポリエステルフィルム
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JP2011245809A (ja) 2010-05-29 2011-12-08 Mitsubishi Plastics Inc 積層ポリエステルフィルム
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WO2014014437A2 (fr) * 2012-07-16 2014-01-23 Empire Technology Development Llc Revêtements organiques hydrophiles auto-renouvelables
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JP5826161B2 (ja) * 2012-12-28 2015-12-02 三菱樹脂株式会社 積層ポリエステルフィルム
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CN112646223A (zh) * 2019-12-27 2021-04-13 富维薄膜（山东）有限公司 高阻隔聚脂薄膜及生产方法

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JP2008255266A (ja) * 2007-04-06 2008-10-23 Toppan Printing Co Ltd プライマー組成物及びこれを用いたガスバリアフィルム
JP2009234009A (ja) * 2008-03-27 2009-10-15 Toray Ind Inc 積層フィルム
JP2010234675A (ja) * 2009-03-31 2010-10-21 Toray Ind Inc 積層ポリエステルフィルムおよびその製造方法
JP2011094125A (ja) * 2009-09-29 2011-05-12 Toray Ind Inc コーティング用組成物および積層フィルム
WO2011068112A1 (fr) * 2009-12-04 2011-06-09 東洋紡績株式会社 Film de résine thermoplastique hautement adhésif
JP2011140216A (ja) * 2009-12-07 2011-07-21 Toyobo Co Ltd 易接着性熱可塑性樹脂フィルム
JP2011140228A (ja) * 2009-12-07 2011-07-21 Toyobo Co Ltd 易接着性熱可塑性樹脂フィルム
JP2011208147A (ja) * 2009-12-07 2011-10-20 Toyobo Co Ltd 易接着性熱可塑性樹脂フィルム
JP2011126158A (ja) * 2009-12-18 2011-06-30 Toyobo Co Ltd 成型用ポリエステルフィルムおよび成型用ハードコートフィルム
JP2011153288A (ja) * 2009-12-28 2011-08-11 Toyobo Co Ltd 易接着性熱可塑性樹脂フィルム
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EP1942132A4 (fr) 2010-06-02
KR20080050484A (ko) 2008-06-05
JPWO2007032295A1 (ja) 2009-03-19
EP1942132B1 (fr) 2011-09-07
TW200720078A (en) 2007-06-01
US20100239868A1 (en) 2010-09-23
US7972700B2 (en) 2011-07-05
TWI406762B (zh) 2013-09-01
ATE523549T1 (de) 2011-09-15
JP4973187B2 (ja) 2012-07-11
EP1942132A1 (fr) 2008-07-09
CN101300294A (zh) 2008-11-05
CN101300294B (zh) 2011-09-07

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